JPWO2013080908A1 - Conductive laminate and display body using the same - Google Patents

Abstract

An object of the present invention is to provide a conductive laminate having good conductivity. A conductive layer having a network structure composed of a linear structure on at least one surface of the substrate, and an opening satisfying the expression (1) among the opening areas of the openings formed by the network structure A conductive laminate having an average value A of 20 μm 2 or less and an opening area variation deviation σ defined by the formula (2) of 26 μm 2 or less. X <Xmax? 0.9 (1) (wherein X represents each opening area and Xmax represents the maximum value of each opening area) σ = {(Σ (X−A) 2) / N } 0.5 (where Σ is i = 1 to N) (2) (where X is the opening area of each opening that satisfies the expression (1), and A is the expression (1)) The average value of the opening area X of the openings, N is the total number of openings satisfying the formula (1).) [Selection] None

Description

  The present invention relates to a conductive laminate having good conductivity. More specifically, the present invention relates to a conductive laminate having a conductive layer having a network structure made of a linear structure and having good conductivity. Furthermore, it is related with the electroconductive laminated body used also for the electrode member used for display relations, such as a liquid crystal display, organic electroluminescence, and electronic paper, and a solar cell module.

  In recent years, conductive members have been used for electrodes in display related products such as touch panels, liquid crystal displays, organic electroluminescence, and electronic paper, and solar cell modules.

  As the conductive member, there is one in which a conductive layer is laminated on a base material. As the conductive layer, a carbon nanotube (hereinafter abbreviated as CNT) is used in addition to those using a conventional conductive thin film such as ITO or a metal thin film. In addition, a network structure is formed by using a linear conductive component such as metal nanowires and metal nanorods to develop conductivity. For example, a conductive laminate in which a layer containing CNT as a conductive component is laminated on a substrate has been proposed (Patent Document 1). Moreover, the electrically conductive laminated body which laminated | stacked the layer which used metal nanowire as the electroconductive component is also proposed (patent document 2). Moreover, the laminated body which controlled the arrangement | sequence of the metal nanorod by using the metal nanorod as an electroconductive component is also proposed (patent document 3). Furthermore, a laminate in which a protective layer is laminated on a conductive layer containing a linear conductive component has also been proposed (Patent Document 4).

Special table 2010-516018 gazette JP 2009-129607 A JP 2006-111675 A International Publication No. 2011/081023 Pamphlet

  However, in the case of using CNT as in Patent Document 1, there is a problem that it is difficult to control the network structure because it is difficult to disperse, and it is difficult to provide a conductive laminate having a low surface resistance value. Even in the case of using a metal nanowire with good conductivity as in Patent Document 2, the surface resistance value is simply laminated on the base material without controlling the dispersion state of the metal nanowire forming the network structure. Since it is difficult to provide a conductive laminate having a low thickness, a special processing step is required when obtaining the conductive laminate. In addition, the one in which the arrangement of metal nanorods is controlled in a specific direction as in Patent Document 3 still has a problem that the surface resistance value is high. Furthermore, as in Patent Document 4, even if a protective layer is provided, the effect of improving the conductivity is low.

  As described above, when a linear material is used for the conductive component, there is a problem that the surface resistance value becomes high due to the network structure and sufficient conductivity cannot be obtained.

  In view of the problems of the prior art, the present invention aims to obtain a good conductive conductive laminate by controlling the network structure of linear conductive components.

In order to solve this problem, the present invention employs the following configuration. That is,
(1) For an opening that has a conductive layer having a network structure composed of a linear structure on at least one side of the substrate, and that satisfies formula (1) among the opening area of the opening formed by the network structure, The average value A of the opening area is 20 μm ² or less, and the variation deviation σ of the opening area defined by the equation (2) is 26 μm ² or less.
X <Xmax × 0.9 (1)
(In the formula, X represents each opening area, and Xmax represents the maximum value of each opening area.)
σ = {(Σ (X−A) ² ) / N} ^0.5 (where Σ is i = 1 to N)
... Formula (2)
(Wherein, X is each opening area of the opening satisfying the expression (1), A is the average value of the opening area X of the opening satisfying the expression (1), and N is the total number of openings satisfying the expression (1). Show.)
Moreover, it is preferable that the electrically conductive laminated body of this invention satisfy | fills the following.
(2) The linear structure is a silver nanowire.
(3) The conductive layer further includes a compound having a structure represented by the following structural formula (1) in the molecule.

(In the formula, Ra (a = 1 to 4) represents H or F. n1 and n2 each independently represents an integer of 1 to 10.)
(4) The conductive layer further includes a polymer matrix.
(5) The said base material is a hydrophilic base material which laminated | stacked the hydrophilic layer containing the compound which has a hydrophilic group in the outermost layer of at least one side.
Furthermore, the present invention also provides the following manufacturing method.
(6) The method for producing a conductive laminate according to any one of (1) to (5), wherein a water-containing dispersion of a linear structure is applied on a substrate and then dried to form a conductive layer. The manufacturing method of the electrically conductive laminated body which is a process which applies to the surface which applied the airflow whose temperature is 25-120 degreeC from the direction of 45-135 degree | times with respect to the application | coating direction.
Moreover, this invention provides the following display bodies.
(7) A display including the conductive laminate according to any one of (1) to (5).
(8) A touch panel incorporating the display body according to (7).
(8) Electronic paper incorporating the display body according to (7).

  ADVANTAGE OF THE INVENTION According to this invention, a conductive laminated body with favorable electroconductivity can be provided.

It is a cross-sectional schematic diagram which shows an example of the electrically conductive laminated body of this invention. It is a schematic diagram which shows an example of the linear structure used for the electrically conductive laminated body of this invention. It is a schematic diagram which shows an example of the opening part formed with the network structure of the linear structure in this invention. It is a cross-sectional schematic diagram which shows an example of the touchscreen which is the one aspect | mode of this invention. It is a cross-sectional schematic diagram which shows an example of the linear structure vicinity of this invention.

[Conductive laminate]
The conductive laminate of the present invention has a conductive layer on at least one side of the substrate. The conductive layer includes a linear structure having a network structure. A linear structure having a network structure works as a so-called conductive component and lowers its resistance value, so that good conductivity is exhibited as a conductive layer.

[Linear structure with network structure]
The conductive component of the conductive layer is a linear structure having a network structure. By making the conductive component into a linear structure having a highly conductive network structure, it is possible to obtain a conductive layer having superior conductivity compared to the blending amount, and thus obtaining a conductive laminate having a low surface resistance value. Can do.

  In the present invention, the linear structure has a network structure. By having the network structure, a conductive path in the surface direction in the conductive layer is formed, and a low surface resistance value can be obtained. In the present invention, the network structure has a distributed structure in which the average number of contacts with another linear structure exceeds at least 1 when viewed with respect to individual linear structures in the conductive layer. Say. At this time, the contact may be in contact with any portion of the linear structure, the end portions of the linear structure are in contact with each other, the end and the portion other than the end of the linear structure are in contact, Portions other than the ends of the structure may be in contact with each other. Here, the contact may mean that the contact is joined or simply in contact. Of the linear structures in the conductive layer, the lines do not contribute to the formation of the network structure (that is, the contacts are 0 and exist independently of other linear structures or network structures). A part of the structure may be present. The network structure can be observed by a method described later.

  Since the conductive component constituting the conductive layer of the conductive laminate of the present invention is composed of a linear structure having a network structure, when the content ratio of the linear structure having a network structure in the conductive layer is below a certain level In some cases, a region where the linear structure does not exist is scattered in the plane, but even if such a region exists, conductivity can be exhibited between any two points.

  The linear structure constituting the network structure can take various ranges for the length of the short axis (diameter of the linear structure) and the length of the long axis (length of the linear structure). The length of the short axis is preferably 1 nm to 1000 nm (1 μm), and the length of the long axis is larger than 10 in aspect ratio (long axis length / short axis length) with respect to the short axis length. What is necessary is just to be such length, and 1 micrometer-100 micrometers (0.1 mm) are preferable. Examples of the linear structure include a fibrous conductor, a nanowire, a needle-like conductor such as a whisker and a nanorod, and the like. Note that the fibrous form means that the aspect ratio = the length of the major axis / the length of the minor axis is greater than 10, and as illustrated by reference numerals 6 and 7 in FIG. It is the shape which has. The nanowire is a linear structure having an arc shape as exemplified by reference numeral 8 in FIG. 2, and the needle shape has a linear shape as exemplified by reference numeral 9 in FIG. It is a linear structure. The linear structure may exist as an aggregate in addition to the case where it exists alone. The aggregated state in the case of existing as an aggregate may be, for example, a state in which the linear structure is not regularly arranged, and may be a randomly aggregated state. May be in a state of being assembled in parallel. As an example of a state in which the surfaces in the major axis direction are gathered in parallel, it is known to be an aggregate called a bundle, and the linear structure may have a similar bundle structure. The average diameter r of the linear structure in the present invention is the diameter r of the single diameter of the linear structure even when the linear structure exists as the aforementioned aggregate. The diameter r of the linear structure is obtained by the following method.

  First of all, the vicinity of the portion of the sample to be observed is embedded in ice, frozen and fixed, and then a rotary microtome manufactured by Japan Microtome Laboratory Co., Ltd. is used, a diamond knife is set at a knife inclination angle of 3 °, and perpendicular to the plane of the laminate Cut in any direction. Next, the obtained conductive region (A) of the cross-section of the laminate was observed using a field emission scanning electron microscope (JSM-6700-F manufactured by JEOL Ltd.) at an acceleration voltage of 3.0 kV and an observation magnification of 10,000 to 100,000. Then, the contrast of the image is appropriately adjusted and observed. For one specimen, images including a cross section of a linear structure obtained from different parts are prepared for 10 visual fields. Next, the diameters of the cross-sections of all the linear structures in the 10 visual fields are obtained, and the total average value thereof is defined as the average diameter r. In this measurement, a magnification that can secure 3 significant digits is selected, and the value is calculated by rounding off the 4th digit.

The material of the linear structure in the present invention contains components such as metal, alloy, metal oxide, metal nitride, metal hydroxide and the like. Examples of the metal include metal elements belonging to 2 to 15 genera in the periodic table of elements. Specifically, gold, platinum, silver, nickel, copper, aluminum, gallium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, manganese, antimony, palladium, bismuth, technetium, rhenium, iron, osmium, cobalt Zinc, scandium, boron, gallium, indium, silicon, germanium, tellurium, tin, magnesium and the like. Examples of the alloy include alloys containing the metal (stainless steel, brass, etc.). Examples of the metal oxide include InO ₂ , SnO ₂ , ZnO, and the like, and these metal oxide composites (InO ₂ Sn, SnO ₂ —Sb ₂ O ₄ , SnO ₂ —V ₂ O ₅ , TiO _2). (Sn / Sb) O ₂ , SiO ₂ (Sn / Sb) O ₂ , K ₂ O—nTiO ₂ — (Sn / Sb) O ₂ , K ₂ O—nTiO ₂ —C, etc.). These may be subjected to a surface treatment. Furthermore, the linear structure includes those obtained by coating or vapor-depositing the surface of an organic compound (for example, plant fiber, synthetic fiber, etc.) or a non-metallic material (for example, inorganic fiber) with the metal or metal oxide. Among these linear structures, silver nanowires can be particularly preferably used from the viewpoint of optical properties such as transparency and conductivity. These metal-based nanowires can be obtained by, for example, the manufacturing methods disclosed in JP-T-2009-505358, JP-A-2009-146747, and JP-A-2009-70660.

  Moreover, a linear structure can also be used individually or in combination of multiple, Furthermore, you may add another electroconductive material of micro-nano size as needed.

[Conductive layer]
The conductive layer of the present invention contains the above-described linear structure having a network structure as an essential component, and as other components, a compound or polymer matrix having the structure of the structural formula (1) described later in the molecule. Furthermore, an additive such as a binder, a dispersant, and a leveling agent contained in the water-containing dispersion of the linear structure described later may be included.

In the conductive layer of the present invention, the average value A of the opening areas obtained for the openings satisfying the expression (1) among the opening areas of the openings formed by the network structure of the linear structures is 20 μm ² or less, and The variation deviation σ of the opening area defined by the equation (2) is 26 μm ² or less. (Hereinafter, the average value A of the opening areas obtained for the openings satisfying the expression (1) among the opening areas of the openings formed by the network structure of the linear structure is defined by the average value A and the expression (2)). (The variation deviation σ of the opening area to be performed may be abbreviated as variation deviation σ.)
X <Xmax × 0.9 (1)
(In the formula, X represents each opening area, and Xmax represents the maximum value of each opening area.)
σ = {(Σ (X−A) ² ) / N} ^0.5 (where Σ is i = 1 to N)
... Formula (2)
(Wherein, X is each opening area of the opening satisfying the expression (1), A is the average value of the opening area X of the opening satisfying the expression (1), and N is the total number of openings satisfying the expression (1). Show.)
When the average value A is 20 μm ² or less, the linear structure becomes dense, and when the variation deviation σ of the opening area is 26 μm ² or less, the network structure of the linear structure becomes uniform, and the in-plane It is estimated that the surface resistance value is lowered and the conductivity is improved by increasing the number of conductive paths. The opening in the present invention is a closed region divided by a linear structure of reference numeral 14 as indicated by reference numeral 15 in FIG. 3, and the average value A and the variation deviation σ are described later. It is defined as a value obtained by the image processing method described in “(3) Average value A and variation deviation σ” in the example. In FIG. 3, the region divided by the linear structure includes a region surrounded only by the linear structure and a region surrounded by the linear structure and the outline of the field of view. The above formula (1) is data calculated in the case where region combination occurs in a portion where the density of the boundary line is low at the time of binarization of the image processing in “(3) average value A and variation deviation σ” of an example described later. Therefore, it is meaningful to remove such a region from the calculation target. In the region surrounded by the linear structure and the outline of the visual field, the above-described region combination is likely to occur in image processing, and the coefficient of 0.9 in the equation (1) also eliminates the combination of regions in such a case. It is set so that it can be done. Specifically, the coefficient A is changed within a numerical range of 1 to 0.7, and the average value A and the variation deviation σ are calculated a plurality of times, respectively, and the maximum effect that the influence of the coupling of the regions as described above does not occur. (The reason for setting the maximum value is that if the value is excessively reduced, the possibility of removing the normal area from the target increases.) That is, when such a coefficient is close to 1, there is an influence of the region in which the average value A and the variation deviation σ are coupled, so the reproducibility of these values is impaired, but as the coefficient is reduced, The reproducibility of these values is improved. A coefficient of 0.9 was adopted based on the reproducibility of such values. The opening area of the openings, preferably the average value A and the variation deviation σ at 10 [mu] m ² or less 17 .mu.m ² or less, and the variation deviation σ is 9 .mu.m ² or less and more preferably an average value A is 5 [mu] m ² or less, more preferably an average The value A is 3 μm ² or less and the variation deviation σ is 4 μm ² or less.

  The conductive layer of the present invention preferably further contains a compound having a structure of the following structural formula (1) in the molecule together with the linear structure.

(In the formula, Ra (a = 1 to 4) represents H or F. n1 and n2 each independently represents an integer of 1 to 10.)
By containing the compound having the structure of the structural formula (1) in the molecule, the surface resistance value is lowered and the conductivity of the conductive laminate can be further improved. The content of the compound having the structure of the structural formula (1) in the molecule depends on the kind of the linear structure and the stacking amount, and also the structure of the compound itself having the structure of the structural formula (1) in the molecule. Therefore, although it cannot limit uniquely, it is preferable that it is 30-100 mass parts with respect to 100 mass parts of linear structures in a conductive layer. If the amount is less than 30 parts by mass, the contained effect may not be obtained. If the amount is more than 100 parts by mass, the uniformity of the network structure of the linear structure may be impaired.

  Examples of the compounds having the structure of the structural formula (1) in the molecule are commercially available, such as Zonyl series Zonyl FSA and Capstone FS-65 made by DuPont.

  The conductive layer of the present invention preferably further contains a polymer matrix together with the linear structure. When processing a conductive laminate for an electrode used for a touch panel or the like, it may be exposed to high temperature or high humidity. By providing the polymer matrix in the conductive layer, the network structure of the linear structure can be protected, and a low surface resistance value can be maintained even in a severe environment such as high temperature and high humidity, and conductivity can be maintained.

[Polymer matrix]
Examples of the component of the polymer matrix include organic or inorganic polymer compounds.

  Examples of the inorganic polymer compound include inorganic oxides, for example, silicon oxides such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra- Tetraalkoxysilanes such as n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltri Methoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxy Silane, n Octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxy Lan, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyl Trialkoxysilanes such as trimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, vinyltriacetoxysilane, methyltriacetyloxysilane, methyltri A sol-gel coating film formed by hydrolysis / polymerization reaction from an alcohol, water, acid, or the like of an organoalkoxysilane such as phenoxysilane, or a sputter deposition film of silicon oxide can be used.

  Examples of organic polymer compounds include thermoplastic resins, thermosetting resins, and photocurable resins. For example, polyester resins, polycarbonate resins, acrylic resins, methacrylic resins, epoxy resins, nylon and benzoguanamine. Such as polyamide resin, ABS resin, polyimide resin, olefin resin such as polyethylene and polypropylene, polystyrene resin, polyvinyl acetate resin, melamine resin, phenol resin, chlorine such as polyvinyl chloride and polyvinylidene chloride (Cl ) -Containing resin, fluorine (F) -containing resin, silicone-based resin, cellulose-based resin, and other organic polymer compounds. At least one type is required based on characteristics and productivity that require these. Or two or more of these may be mixed, but preferably , The carbon contributing to the polymerization reaction - is preferably a compound having two or more carbon-carbon double bond group are those composed of a polymer containing polymerization reaction structure. Such a polymer comprises a composition comprising a monomer, an oligomer, or a polymer having two or more carbon-carbon double bond groups that contribute to the polymerization reaction, and a carbon-carbon double bond in the carbon-carbon double bond group. It can be obtained by forming a carbon-carbon single bond by carrying out a polymerization reaction as a reaction point.

Examples of the functional group containing a carbon-carbon double bond group include an isopropenyl group, an isopentenyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a methacryl group, an acrylamide group, and a methacrylamide group. , Arylidene group, allylidine group, vinyl ether group, or carbon-carbon double bond group with a halogen element such as fluorine or chlorine bonded (for example, vinyl fluoride group, vinylidene fluoride group, vinyl chloride group, chloride) Vinylidene groups, etc.), carbon-carbon double bond groups in which a substituent having an aromatic ring such as a phenyl group or a naphthyl group is bonded (for example, styryl groups), butadienyl groups (for example, CH ₂ ═C _{(R 1) -C (R 2} ) = CH-, CH 2 = C (R 1) -C (= CH 2) - (R 1, R 2 H or CH ₃₎₎ group having a conjugated polyene structure as, and the like. In consideration of the characteristics and productivity required from these, one type or a mixture of two or more types may be used.

  Examples of the compound having two or more carbon-carbon double bond groups that contribute to the polymerization reaction include pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol ethoxytriacrylate, penta Erythritol ethoxytrimethacrylate, pentaerythritol ethoxytetraacrylate, pentaerythritol ethoxytetramethacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pen Methacrylate, Dipentaerythritol hexaacrylate, Dipentaerythritol hexamethacrylate, Trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, Trimethylolpropane ethoxytriacrylate, Trimethylolpropane ethoxytrimethacrylate, Ditrimethylolpropane triacrylate, Ditrimethylolpropane triacrylate Methacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, glycerin propoxytriacrylate, glycerin propoxytrimethacrylate, and compounds having a cyclic skeleton such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring in the molecule (for example, , Triac relay・ Trimethacrylate ・ Tetraacrylate ・ Tetramethacrylate ・ Pentaacrylate ・ Pentamethacrylate ・ Hexaacrylate ・ Hexamethacrylate etc.) and compounds obtained by modifying some of these compounds (eg 2-hydroxypropanoic acid modified with 2-hydroxypropanoic acid etc.) Modified pentaerythritol triacrylate, 2-hydroxypropanoic acid modified pentaerythritol trimethacrylate, 2-hydroxypropanoic acid modified pentaerythritol tetraacrylate, 2-hydroxypropanoic acid modified pentaerythritol tetramethacrylate, and a silicone triacrylate having a silicone skeleton introduced, Silicone trimethacrylate, silicone tetraacrylate, silicone tetramethacrylate, silicone paint Acrylate, silicone pentamethacrylate, silicone hexaacrylate, silicone hexamethacrylate, etc.) and other compounds having a vinyl group and / or vinylidene group in the skeleton (for example, urethane triacrylate, urethane trimethacrylate, urethane having a urethane skeleton) Tetraacrylate, urethane tetramethacrylate, urethane pentaacrylate, urethane pentamethacrylate, urethane hexaacrylate, urethane hexamethacrylate, polyether triacrylate with ether skeleton, polyether trimethacrylate, polyether tetraacrylate, polyether tetramethacrylate, polyether penta Acrylate, polyether pentamethacrylate, poly -Tetrahexaacrylate, Polyetherhexamethacrylate, Epoxytriacrylate with epoxy-derived skeleton, Epoxytrimethacrylate, Epoxytetraacrylate, Epoxytetramethacrylate, Epoxypentaacrylate, Epoxypentamethacrylate, Epoxyhexaacrylate, Epoxyhexamethacrylate, Ester skeleton Polyester triacrylate, polyester trimethacrylate, polyester tetraacrylate, polyester tetramethacrylate, polyester pentaacrylate, polyester pentamethacrylate, polyester hexaacrylate, polyester hexamethacrylate, etc.). In consideration of applications, required characteristics, productivity, and the like, compositions containing two or more of polymerized as a single substance or polymerized as a single substance, and / or a dimer or more obtained by copolymerization of two or more. Although the composition containing this oligomer can be used, it is not specifically limited to these. Among these compounds, a compound having 4 or more carbon-carbon double bond groups that contribute to the polymerization reaction, that is, a tetrafunctional or more functional compound can be more preferably used. Examples of the tetrafunctional or higher functional compound include the tetrafunctional tetraacrylate, tetramethacrylate, pentafunctional pentaacrylate, pentamethacrylate, hexafunctional hexaacrylate, hexamethacrylate, and the like.

  These compounds are commercially available, for example, Kyoeisha Chemical Co., Ltd. light acrylate series, light ester series, epoxy ester series, urethane acrylate AH series, urethane acrylate AT series, urethane acrylate UA series, Daicel -"EBECRYL" (registered trademark) series (for example, EBECRYL1360) manufactured by Cytec Corporation, PETIA, TMPTA, TMPEOTA, OTA 480, DPHA, PETA-K, "Fure Cure" (registered trademark) series manufactured by Soken Chemical Co., Ltd. "LIODURAS" (registered trademark) series manufactured by Toyo Ink Manufacturing Co., Ltd., "Folcede" (registered trademark) series manufactured by China Paint Co., Ltd., EXP series manufactured by Matsui Kagaku Co., Ltd. Shin-Etsu Chemical Co., Ltd. of X-12-2456 series, and the like.

[Base material]
Specific examples of the material for the base material in the conductive laminate of the present invention include transparent resin and glass. Examples of the resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamide, polyimide, polyphenylene sulfide, aramid, polyethylene, polypropylene, polystyrene, polylactic acid, polyvinyl chloride, polycarbonate, polymethyl methacrylate, and the like. Contains chlorine (Cl) such as acrylic and methacrylic resins, cycloaliphatic acrylic resins, cycloolefin resins, triacetyl cellulose, ABS, polyvinyl acetate, melamine resins, phenolic resins, polyvinyl chloride and polyvinylidene chloride Resin, fluorine (F) -containing resin, silicone resin and a mixture and / or copolymerization of these resins. As the glass, ordinary soda glass can be used. Moreover, these several base materials can also be used in combination. For example, a composite substrate such as a substrate in which a resin and glass are combined and a substrate in which two or more kinds of resins are laminated may be used. About the shape of a base material, even if it is a film which can be wound up by thickness 250 micrometers or less, a base material exceeding thickness 250 micrometers may be sufficient. From the viewpoint of cost, productivity, handleability, etc., a resin film of 250 μm or less is preferable, more preferably 190 μm or less, still more preferably 150 μm or less, and particularly preferably 100 μm or less. When using a resin film as a base material, what was made into the film by unstretching, uniaxial stretching, and biaxial stretching of resin can be applied. Among these resin films, from the viewpoint of moldability to a substrate, optical properties such as transparency, productivity, etc., polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and mixing with PEN and A copolymerized PET film or polypropylene film can be preferably used.

In this invention, it is preferable that it is a hydrophilic base material which laminated | stacked the hydrophilic layer containing the compound which has a hydrophilic group in the outermost layer of the at least single side | surface of these base materials. In the case of forming a conductive layer by applying a water-containing dispersion of a linear structure, which will be described later, to form a conductive layer, the opening area at the opening formed by the network structure of the linear structure is a hydrophilic substrate. The average value A and the variation deviation σ can be in a preferable range, and it becomes easy to obtain a conductive laminate having a low surface resistance value and good conductivity. Examples of the compound having a hydrophilic group include those having a hydrophilic group in the structure of the polymer matrix described above and the resin used for the substrate, but are not particularly limited. Examples of hydrophilic groups include hydroxyl groups, carboxylic acid groups, phosphoric acid groups, amino groups, quaternary ammonium bases, sulfonic acid groups, and some of these hydrophilic groups have counter cations such as Na ⁺ and K ^+. state (e.g., -ONa, -COONa, _-SO 3 Na, etc.) and the like, may be mixed and these one or two or more. Among these functional groups, a carboxylic acid group, a sulfonic acid group, and a part of each hydrophilic group that easily impart hydrophilicity have a counter cation such as Na ⁺ or K ⁺ (—COONa, —SO ₃ Na) Can be preferably used.

[Method for producing conductive laminate]
The method for producing the conductive laminate of the present invention is not particularly limited, and only the conductive material (linear structure) or the conductive material (linear structure) and the above-described polymer matrix are mixed on the base material. A conductive layer may be formed by laminating one, or a conductive layer is laminated by first forming only a conductive material (linear structure) on a substrate in advance and then forming a polymer matrix. There is no particular limitation.

[Method of forming conductive layer]
As a method for forming a conductive layer on a substrate in the present invention, an optimal method may be selected depending on the type of linear structure or matrix, cast, spin coating, dip coating, bar coating, spraying, blade coating, Common methods such as wet coating methods such as slit die coating, gravure coating, reverse coating, screen printing, mold coating, printing transfer, and inkjet can be used. Among them, a slit die coat which can uniformly laminate the conductive layer and hardly damages the substrate, or a wet coat method using a micro gravure which can form the conductive layer uniformly and with high productivity is preferable. In forming the conductive layer on the base material, a conductive component having a network structure made of a conductive material (linear structure) is placed on the base material in advance, and then a matrix is placed on the conductive material (linear structure). And a conductive layer may be formed by combining the conductive material (linear structure) and the matrix in advance to form a conductive matrix composition, and the conductive matrix composition is formed on the substrate. A conductive layer including a conductive component having a network structure may be formed by stacking. The conductive material (linear structure) may be a single material or a mixture of a plurality of materials. Similarly, the matrix may be composed of a single material or a mixture of a plurality of materials.

  In the present invention, particularly preferably, in the step of appropriately selecting the above-described method and applying the water-containing dispersion of the linear structure on the substrate and then drying to form a conductive layer, the drying step is in the coating direction. On the other hand, it is a manufacturing method of the electrically conductive laminated body which is a process applied to the surface which applied the airflow whose temperature is 25-120 degreeC from the direction of 45-135 degree.

  By adopting such a method, the average value A and the variation deviation σ of the opening area in the openings formed by the network structure of the linear structure can be set within a preferable range, and the surface resistance is low and the conductivity is good. It becomes easy to obtain a conductive laminate. In addition, the water-containing dispersion of the linear structure may contain additives such as a binder, a dispersant, and a leveling agent in addition to the linear structure and water as a solvent. The point which is applied to the surface where the airflow is applied from the direction of 45 to 135 ° with respect to the application direction will be described. After applying the water-containing dispersion liquid of the linear structure on the substrate, the network structure is likely to be uniform by applying the airflow from the direction of 45 to 135 ° to the coating direction, and the variation in the opening The deviation σ can be reduced. Preferably, the direction is 60 to 120 ° with respect to the coating direction, more preferably the direction is 85 to 95 °. Conversely, if the angle is less than 45 ° or larger than 135 ° with respect to the coating direction, the effect may not be obtained. . Then, the point that the temperature of the airflow in that case is 25-120 degreeC is demonstrated. When the temperature of the airflow in the drying process is 25 to 120 ° C., the linear structure can be uniformly dispersed in the surface of the conductive layer without aggregation, and the average value A of the opening area and the variation deviation σ can be set in a desired region. Easy to adjust. The temperature of the airflow is preferably 30 to 100 ° C., more preferably 50 to 90 ° C. When the temperature is less than 25 ° C., the drying of the water-containing dispersion of the linear structure may be slow, and the opening On the other hand, when the temperature is higher than 120 ° C., the aqueous solvent tends to evaporate rapidly and tends to be dried unevenly in the plane of the conductive layer, and the average opening area The value A and the variation deviation σ may increase. The temperature adjusting means can be selected according to the purpose and application, and examples thereof include a hot plate, a hot air oven, an infrared oven, and microwave irradiation with a frequency of 300 megahertz to 3 terahertz, but are not limited thereto. In addition, the temperature of airflow means the temperature in the upper 10 mm position of the apply | coated surface.

  The method for forming the matrix of the conductive layer of the conductive laminate in the present invention is formed by reacting the composition containing the components of the polymer matrix described above. Formation of a polymer matrix by reaction in such a case is referred to as curing in this specification. Examples of a method for curing a composition containing a component of a polymer matrix include heat curing and photocuring by irradiation with an active electron beam such as ultraviolet light, visible light, and electron beam (hereinafter referred to as photocuring). In the case of heat curing, while it takes time to heat the entire system to the curing start temperature, in the case of photocuring, a photocuring initiator as described later (hereinafter referred to as a photoinitiator) is contained, By irradiating an active electron beam thereto, active species can be generated simultaneously in the entire system, so that the time required to start curing can be shortened, and the curing time can also be shortened. For this reason, photocuring is more preferable. Here, the photoinitiator is an active species such as radical species, cation species, anion species, etc., which are active species that absorb an active electron beam such as ultraviolet light, visible light, or electron beam and initiate a reaction. Is a substance that initiates a chemical reaction. Usable photoinitiators include, for example, benzophenone series such as benzophenone, hydroxybenzophenone, 4-phenylbenzophenone, benzoin series such as benzyldimethyl ketal, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 2-methyl 1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone-1, α-hydroxyketone, α-aminoketone, thioxanthone, such as isopropylthioxanthone, 2-4-diethylthioxanthone, methylphenylglyoxylate, and the like. Viewpoint of color sighting, coloring degree, etc. Therefore, one or more of these photoinitiators can be used in combination.

  Commercially available products of such photoinitiators include Ciba “IRGACURE (registered trademark)” 184 (manufactured by Ciba Japan) as 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl 1 [4- (methylthio) phenyl. Ciba “IRGACURE” (registered trademark) 907 (manufactured by Ciba Japan), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) as 2-morpholinopropan-1-one -As butanone-1, Ciba "IRGACURE" (registered trademark) 369 (manufactured by Ciba Japan Co., Ltd.) and the like can be mentioned.

Depending on the type and nature of the matrix, the type of the active electron beam is appropriately selected, or the photoinitiator alone is selected from the selected type of the active electron beam, or two or more different absorption wavelength regions are contained, The conductive laminate of the present invention can also be obtained by adjusting the irradiation amount of the active electron beam or by appropriately combining these. In particular, the method of adjusting the irradiation amount of the active electron beam is preferably used because it is relatively easy to implement. The method of adjusting the irradiation amount can be controlled relatively easily by changing the conditions (output conditions, etc.) of the irradiation body such as the lamp that irradiates the active electron beam. In addition, the irradiation time can be shortened by changing the irradiation distance between the irradiation body such as the lamp and the non-irradiation body or adjusting the transport speed of the non-irradiation body in the production of the conductive laminate of the present invention. Thus, the integrated dose can be controlled. Dose of accumulation of the active electron beam is preferably from 300 mJ / cm ² or less, more preferably 150 mJ / cm ² or less, more preferably 100 mJ / cm ² or less. The lower limit value of the integrated irradiation amount of the active electron beam is not particularly limited, but if it is less than 1 mJ / cm ² , defects such as insufficient curing of the matrix may occur, and it is preferably 1 mJ / cm ² or more. In addition, when irradiating the active electron beam, it is also effective to use a specific atmosphere in which the oxygen concentration is lowered, such as in an atmosphere substituted with an inert gas such as nitrogen or argon, or in an atmosphere deoxygenated. In addition, it is preferable to set the integrated irradiation amount of the active electron beam in a specific atmosphere with a low oxygen concentration.

  The conductive laminate according to the present invention is preferably a transparent conductive laminate having a total light transmittance of 80% or more based on JIS K7361-1: 1997 when incident from the conductive layer side. The touch panel incorporating the conductive laminate of the present invention exhibits excellent transparency, and the display on the display provided in the lower layer of the touch panel using the transparent conductive laminate can be clearly recognized. The transparency in the present invention means that the total light transmittance based on JIS K7361-1: 1997 when entering from the conductive layer side is 80% or more, preferably 85% or more, more preferably 90% or more. As a method for increasing the total light transmittance, for example, a method for increasing the total light transmittance of a substrate to be used, a method for reducing the film thickness of the conductive layer, and a method in which the conductive layer becomes an optical interference film. And the like.

  As a method for increasing the total light transmittance of the base material, a method of reducing the thickness of the base material or a method of selecting a base material made of a material having a large total light transmittance can be mentioned. As the substrate in the transparent conductive laminate of the present invention, a substrate having a high visible light total light transmittance can be suitably used. Specifically, the total light transmittance based on JIS K7361-1: 1997 is 80% or more. And more preferably 90% or more of transparency, and any of those described in the above-mentioned [Substrate] can be used as appropriate.

  In the present invention, the surface opposite to the conductive side (the side on which the conductive layer is laminated in the present invention) with respect to the base material is provided with wear resistance, high surface hardness, solvent resistance, stain resistance, etc. The provided hard coat treatment may be performed.

  Next, a description will be given of a method of laminating the conductive layer so as to be an optical interference film.

  The conductive material (linear structure) reflects and absorbs light due to the physical properties of the conductive component itself. Therefore, in order to increase the total light transmittance of the transparent conductive laminate including the conductive layer provided on the substrate, the matrix is made of a transparent material and the conductive layer is an optical interference film. It is effective to lower the average reflectance at the side wavelength of 380 to 780 nm to 4% or less, preferably to 3% or less, and more preferably to 2% or less. When the average reflectance is 4% or less, a performance with a total light transmittance of 80% or more when used for touch panel applications can be obtained with good productivity.

In the conductive laminate of the present invention, the surface resistance value on the conductive layer side is preferably 1 × 10 ⁰ Ω / □ or more and 1 × 10 ⁴ Ω / □ or less, more preferably 1 × 10 ¹ Ω / □. □ or more and 1.5 × 10 ³ Ω / □ or less. By being in this range, it can be preferably used as a conductive laminate for a touch panel. That is, if it is 1 × 10 ⁰ Ω / □ or more, power consumption can be reduced, and if it is 1 × 10 ⁴ Ω / □ or less, the influence of errors in the coordinate reading of the touch panel can be reduced.

  Various additives can be added to the base material and / or the conductive layer used in the present invention within a range not impairing the effects of the present invention. Examples of additives include organic and / or inorganic fine particles, crosslinking agents, flame retardants, flame retardant aids, heat stabilizers, oxidation stabilizers, leveling agents, slip activators, antistatic agents, ultraviolet absorbers, Light stabilizers, nucleating agents, dyes, fillers, dispersants, coupling agents and the like can be used.

  The conductive laminate of the present invention can be preferably used by incorporating it into a display body, particularly a touch panel and electronic paper. Among them, a schematic cross-sectional view showing an example of a touch panel is shown in FIG. The touch panel of the present invention incorporates the conductive laminate (for example, FIG. 1) of the present invention in which conductive layers having a network structure composed of linear structures are laminated alone or in combination with other members. Examples thereof include a resistive touch panel and a capacitive touch panel. As shown in FIG. 2, the conductive layer of the conductive laminate of the present invention includes a linear structure such as 6, 7, 8, and 9, and has a network structure having contacts 11, 12, and 13. ing. A touch panel on which the conductive laminate of the present invention is mounted is formed by joining and laminating a conductive laminate 16 with a bonding layer 19 such as an adhesive or an adhesive as shown in FIG. A hard coat layer 21 laminated on the screen side base material 20 and the screen side base material of the touch panel is provided. Such a touch panel is used, for example, by attaching a lead wire and a drive unit, etc., and incorporating it on the front surface of the liquid crystal display.

  Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the following examples.

[Evaluation method]
First, an evaluation method in each example and comparative example will be described.

(1) Structure of conductive component (shape), state of network structure of conductive component Using insulation resistance meter (manufactured by Sanwa Denki Keiki Co., Ltd., DG6) To identify the conductive surface of the sample.

  Next, the surface of each of the conductive region (A) and the non-conductive region (B) of the sample was scanned with a scanning transmission electron microscope (Hitachi Scanning Electron Microscope HD-2700, manufactured by Hitachi High-Technologies Corporation) or a field emission scanning electron microscope ( Using JSM-6700-F (manufactured by JEOL Ltd.), the acceleration voltage was 3.0 kV, the observation magnification and the image contrast were appropriately adjusted, and observation was performed at each magnification.

  If observation by the above method is difficult, then a color 3D laser microscope (VK-9700 / 9710 manufactured by Keyence Corporation), an observation application (VK-H1V1 manufactured by Keyence Corporation), and a shape analysis application (Keyence Corporation) Using VK-H1A1), the attached standard objective lens 10X (Nikon Corporation CF IC EPI Plan 10X), 20X (Nikon Corporation CF IC EPI Plan 20X), 50X (Nikon Corporation CF) IC EPI Plan Apo 50X), 150X (CF IC EPI Plan Apo 150X manufactured by Nikon Corporation) was used to observe the same position on the conductive side at each magnification, and image analysis was performed from the image data.

(2) Identification of conductive component The conductive layer was peeled from the sample and dissolved in a solvent to be dissolved. If necessary, apply general chromatography such as silica gel column chromatography, gel permeation chromatography, liquid high-speed chromatography, etc., and separate and purify each into a single substance for the following qualitative analysis .

  Thereafter, the conductive component was appropriately concentrated and diluted to prepare a sample. Subsequently, the component contained in a sample was specified using the following evaluation methods.

  Analysis methods were combined with the following analysis methods, and those that could be measured with fewer combinations were preferentially applied.

Nuclear magnetic resonance spectroscopy ( ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, ¹⁹ F-NMR), two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR), infrared spectrophotometry (IR), Raman Spectroscopy, various mass spectrometry (gas chromatography-mass spectrometry (GC-MS), pyrolysis gas chromatography-mass spectrometry (pyrolysis GC-MS), matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) ), Time of Flight Mass Spectrometry (TOF-MS), Time of Flight Matrix Assisted Laser Desorption / Ionization Mass Spectrometry (MALDI-TOF-MS), Dynamic Secondary Ion Mass Spectrometry (Dynamic-SIMS), Time of Flight Type II Secondary ion mass spectrometry (TOF-SIMS), other static secondary ion mass spectrometry (Static-SIMS), etc.) X-ray diffraction (XRD), neutron diffraction (ND), low-energy electron diffraction (LEED), fast reflection electron diffraction (RHEED), atomic absorption spectrometry (AAS), ultraviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), fluorescent X-ray elemental analysis (XRF), inductively coupled plasma emission spectroscopy (ICP-AES), electron microanalysis (EPMA), charged particles Excitation X-ray spectroscopy (PIXE), low energy ion scattering spectroscopy (RBS or LEIS), medium energy ion scattering spectroscopy (MEIS), high energy ion scattering spectroscopy (ISS or HEIS), gel permeation chromatography (GPC) , Transmission electron microscope-energy dispersive X-ray spectroscopic analysis (TEM-EDX), scanning electron microscope-energy dispersive X-ray spectroscopic analysis (SEM-EDX), gas chromatography (GC) and other elemental analysis.

(3) Average value A and variation deviation σ
The conductive layer side of the sample is a color 3D laser microscope (VK-9700 / 9710 manufactured by Keyence Corporation), observation application (VK-H1V1 manufactured by Keyence Corporation), and shape analysis application (VK-H1A1 manufactured by Keyence Corporation). Using the attached standard objective lens 150X (CF IC EPI Plan Apo 150X manufactured by Nikon Corporation), the surface of the conductive side was observed at a magnification of 3000 times, and the range of 70.656 μm × 94.208 μm was 768 pixels × 1024. The image was captured as a pixel image and analyzed. For image analysis, prepare 5 samples for each level, observe 10 fields per sample, that is, 50 fields per level, analyze each 50 fields by the following method, obtain the data of 50 fields and average The value was calculated. (In this example, evaluation was performed with the magnification and resolution described above, but depending on the type of linear structure, the length of the major axis and the length of the minor axis (average diameter r) differed, and observation was performed at the magnification. Is difficult, the attached standard objective lens 10X (Nikon Corporation CF IC EPI Plan 10X), 20X (Nikon Corporation CF IC EPI Plan 20X), 50X (Nikon Corporation CF IC EPI Plan 20X) Change to one of Apo 50X) to reduce the magnification, or change to objective lens 200X (CF IC EPI Plan Apo 200X made by Nikon Corporation) to increase the magnification to the same resolution and capture the image data in the same way In terms of resolution, it is suitable that the size of one pixel is a region of 0.1 μm in length × 0.1 μm in width to be evaluated. Not.)
Specifically, the image processing was performed in the following environment and procedure.
OS: “Windows” (registered trademark) XP
CPU: “Celeron” (registered trademark) 3.4 GHz
Memory: 512MB
Software used: Image processing library HALCON (Ver. 9.0, manufactured by MVtec)
First, image processing is performed by reading image data, then performing contour enhancement (processing in the order of differentiation filter (emphasize) and edge enhancement filter (shock_filter)) and then binarizing. . The differential filter “emphasize” and the edge enhancement filter “shock_filter” used for edge enhancement are image processing filters included in the HALCON of the image processing library. For binarization, an average value of the luminance of the entire image is obtained, an offset of 10 is applied to the average value, a portion showing a larger value is defined as a portion where the linear structure exists, and the linear structure Replace the gray value of the region where the pixel exists with 255, replace the gray value of the other region (opening) with 0, perform expansion / contraction, thinning, and connect consecutive pixels with a gray value of 0, Extracted as an opening.

Next, the opening area X of each opening in one field of view extracted by image processing is obtained, and the opening that satisfies Expression (1) among the openings in one field of view is expressed by Expression (2). The variation deviation σ of the opening area was calculated.
X <Xmax × 0.9 (1)
Here, Xmax is the maximum value of the aperture area in the image data within one field of view.
σ = {(Σ (X−A) ² ) / N} ^0.5 (where Σ is i = 1 to N)
... Formula (2)
Here, A is the average value of the opening areas X of the openings satisfying the expression (1) in one field of view, and N is the total number of openings satisfying the expression (1) in one field of view.

(4) Surface resistance value R ₀
The surface resistance value on the conductive layer side of the conductive laminate was measured at a central portion of a 100 mm × 50 mm sample by an eddy current method using a non-contact type resistivity meter (NC-10 manufactured by Napson Co., Ltd.). An average value was calculated for 5 samples, and this was defined as a surface resistance value R ₀ [Ω / □]. When the surface resistance value was not obtained exceeding the detection limit, it was then measured by the following method.

Using a high resistivity meter (Hiresta-UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation), a ring type probe (URS probe MCP-HTP14 manufactured by Mitsubishi Chemical Corporation) is connected and 100 mm × 100 mm in a double ring system. The central part of the sample was measured. An average value was calculated for 5 samples, and this was defined as a surface resistance value R ₀ [Ω / □]. In the present invention, the practically usable range as the surface resistance value is set to 1 × 10 ⁸ [Ω / □] or less, and this or less is regarded as acceptable.

(5) Total light transmittance Using a turbidimeter (cloudiness meter) NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), based on JIS K7361-1: 1997, the total light transmittance in the thickness direction of the conductive laminate is obtained. Measurement was performed by making light incident from the conductive layer side. It measured about 5 samples, calculated the average value of 5 samples, and made this the total light transmittance of each level. In this measurement, a magnification that can secure one significant digit was selected, and the value was calculated by rounding off the second digit. In addition, in this invention, 76.5% or more which is the range which can be used practically as a total light transmittance was made into the pass.

(6) Durability The surface resistance value _R0 obtained in (4) was used as the initial surface resistance value. Next, an acceleration test was carried out for 24 hours in a high temperature and high humidity condition at a temperature of 60 ° C. and a humidity of 90% RH in a thermostat perfect oven (PH-400 manufactured by Espec Corp.). After the acceleration test, the surface resistance value of five samples was measured in the same manner as before the acceleration test. The average value of 5 samples was calculated and used as the surface resistance value R after heating. As a change in surface resistance value before and after heating, a ratio R / R ₀ between the initial surface resistance value R ₀ and the surface resistance value R after heating was determined. In addition, R / R ₀ is 1.0 or more, and it means that durability is high, and it is maintaining electroconductivity, so that it is close to 1.0, and the thing with the highest durability is surface resistance before and behind heating. The value does not change, that is, R / R ₀ is 1.0. Conversely, the larger R / R ₀ means that the durability against heat is lower. In addition, in this invention, the range which can be used practically as R / _R0 was 2.0 or less, and this or less was set as the pass.

[material]
<Base material>
The base materials used in each example and comparative example are shown below.

(1) Substrate A
・ Polyethylene terephthalate film ("Lumirror" (registered trademark) T60 manufactured by Toray Industries, Inc.)
・ Thickness 125μm
-No hydrophilic layer (2) Base material B
A hydrophilic substrate in which the following polyester resin hydrophilic layers are laminated on both surfaces of the substrate A.
・ Thickness 125μm
Polyester resin hydrophilic layer <Polyester resin (a1)> and <Polyester resin (a2)> below were mixed at a mass ratio of 1: 1 to obtain <Polyester resin (A)>. Next, a hydrophilic layer composition containing 100 parts by mass of the <polyester resin (A)> and 50 parts by mass of the following <melamine-based crosslinking agent (B)> was obtained. This hydrophilic layer composition was laminated on the base material A at a thickness of 0.1 μm (per side, hereinafter the same unless otherwise specified) to obtain a base material B.
<Polyester resin (a1)>
-Component ratio of the following (i) / (ii) / (iii) / (iv) = 12/76/12/100 [mol%]
(I) 5-sodium sulfoisophthalic acid (compound having a hydrophilic group)
(Ii) 2,6-naphthalenedicarboxylic acid (compound having a hydrophilic group)
(Iii) Trimellitic acid (compound having a hydrophilic group)
(Iv) Ethylene glycol <Polyester resin (a2)>
-Component ratio of the following (i) / (ii) / (iii) = 76/24/100 [mol%]
(I) Terephthalic acid (compound having a hydrophilic group)
(Ii) trimellitic acid (compound having a hydrophilic group)
(Iii) Ethylene glycol <Melamine-based cross-linking agent (B)>
・ Methylolated melamine resin (3) Base material C
A hydrophilic base material in which the following acrylic resin hydrophilic layers are laminated on both surfaces of the base material A.
・ Thickness 125μm
-Hydrophilic layer of acrylic resin A composition for a hydrophilic layer containing 100 parts by mass of the following <acrylic resin (A)> and 50 parts by mass of the following <melamine crosslinking agent (B)> was obtained. This hydrophilic layer composition was laminated on the substrate A with a thickness of 0.1 μm to form a substrate C.
<Acrylic resin (A)>
-Component ratio of the following (i) / (ii) / (iii) / (iv) / (v) = 55/38/3/2/2 [mol%]
(I) methyl methacrylate (ii) ethyl acrylate (iii) N-methylol acrylamide (iv) 2-hydroxyethyl methacrylate (compound having a hydrophilic group)
(V) Acrylic acid (compound having a hydrophilic group)
<Melamine crosslinking agent (B)>
・ Methylolated melamine resin <conductive material>
Each conductive material in each example and comparative example is shown below.

(1) Conductive material A “silver nanowire”
Silver nanowire conductive material (short axis: 50 to 100 nm, long axis: 20 to 40 μm).

(2) Conductive material B "Copper nanowire"
Copper nanowire conductive material (short axis: 10 to 20 nm, long axis: 1 to 100 μm) obtained by the method described in Production Example 1 and Example 2 of JP-A-2002-266007.

(3) Conductive material C “Silver nanowire / copper nanowire mixed conductive material”
A silver nanowire / copper nanowire mixed conductive material obtained by mixing the conductive material A “silver nanowire” and the conductive material B “copper nanowire” in a mass ratio of 6: 4.

(4) Conductive material D “Acicular silicon dioxide-based / ATO (antimony-doped tin oxide) composite compound conductive material”
Needle-like silicon dioxide-based / ATO (antimony-doped tin oxide) composite compound (“Dentor” (registered trademark) TM100, manufactured by Otsuka Chemical Co., Ltd., short axis: 700 to 900 nm, long axis: 15 to 25 μm) conductive material.
<Matrix, additive>
The materials used for the matrix and additive of each Example and Comparative Example are shown below.

(1) Matrix material A
An acrylic composition containing a compound having two or more carbon-carbon double bond groups contributing to the polymerization reaction as an acryloyl group (“Fure Cure” (registered trademark) HC-6, manufactured by Soken Chemical Co., Ltd., solid content concentration 51) mass%).

(2) Additive A
A compound having a structure of the structural formula (1) in the molecule (Zonyl FSA manufactured by DuPont, USA).

Example 1
As the aqueous dispersion containing the conductive material A, a silver nanowire dispersion (“ClearOhm” (registered trademark) Ink-A AQ manufactured by Cambrios, USA) was used. This silver nanowire dispersion liquid was diluted so that the concentration of silver nanowires was 0.042% by mass to prepare a silver nanowire dispersion coating liquid.

  Next, this silver nanowire-dispersed coating liquid (conductive composition) was applied to one side of the substrate A using a bar coater count 8 manufactured by Matsuo Sangyo Co., Ltd., and the applied surface was 30 ° with respect to the coating direction. A conductive layer was formed by applying hot air of 120 ° C. from the direction of 60 seconds for 60 seconds and drying by heating to obtain a conductive laminate.

(Example 2)
A silver nanowire-dispersed coating liquid having a concentration of silver nanowires of Example 1 of 0.042% by mass was prepared. In this silver nanowire dispersion coating liquid, additive A was mixed so that the component amount of additive A was 65 parts by mass with respect to 100 parts by mass of silver nanowires to obtain a silver nanowire / additive mixture dispersion. .

  Next, this silver nanowire / additive mixture dispersion (conductive composition) was applied to one side of the substrate A using a bar coater count 8 manufactured by Matsuo Sangyo Co., Ltd. On the other hand, a conductive layer was formed by applying hot air of 120 ° C. from a direction of 30 ° for 60 seconds and drying by heating to obtain a conductive laminate. In this conductive laminate, the compound having the structure of the structural formula (1) in the molecule is included in the conductive layer, so that the average value A of the opening area and the variation deviation σ thereof are reduced, and no compound is included. The surface resistance value decreased.

(Example 3)
The silver nanowire / additive mixture dispersion of Example 2 was prepared.

  Next, this silver nanowire / additive mixture dispersion (conductive composition) was applied to one side of the substrate B using a bar coater count 9 manufactured by Matsuo Sangyo Co., Ltd. On the other hand, a conductive layer was formed by applying hot air of 120 ° C. from a direction of 30 ° for 60 seconds and drying by heating to obtain a conductive laminate. In this conductive laminate, by forming a conductive layer on a hydrophilic substrate, the average value A of the opening area and the variation deviation σ thereof are reduced, which is more than in Example 2 using the substrate A having no hydrophilic layer. The surface resistance value decreased.

Example 4
A conductive layer was formed in the same manner as in Example 3 except that a conductive layer was formed by applying hot air of 80 ° C. from a direction of 90 ° to the coated surface for 60 seconds and drying by heating. A laminate was obtained. In this conductive laminate, the average value A of the opening area and the variation deviation σ thereof were reduced by changing the conditions at the time of heating and drying to preferable conditions, and the surface resistance value was lower than that of Example 3 before the change.

(Example 5)
The silver nanowire / additive mixture dispersion of Example 2 was prepared.

  Next, this silver nanowire / additive mixture dispersion (conductive composition) was applied to one side of the substrate C using a bar coater count 10 manufactured by Matsuo Sangyo Co., Ltd. On the other hand, a conductive layer was formed by applying hot air at 80 ° C. for 60 seconds from the direction of 90 ° and drying by heating to obtain a conductive laminate. By changing the number of the bar coater and changing the coating amount of the silver nanowire / additive mixture dispersion (conductive composition), this conductive laminate decreases the average value A of the opening area and its variation deviation σ. The surface resistance value was lower than that in Example 4 before the change.

(Example 6)
A conductive layer was formed in the same manner as in Example 5 except that the substrate B was used, and this was used as a conductive laminate. In this conductive laminate, the average value A of the opening area and the variation deviation σ thereof are reduced by changing the type of the hydrophilic substrate, and the surface resistance value is higher than that in Example 5 using the substrate C having a different hydrophilic layer. Decreased.

(Example 7)
The silver nanowire / additive mixture dispersion of Example 2 was prepared.

  Next, this silver nanowire / additive mixture dispersion (conductive composition) was applied to one side of the substrate C using a bar coater count 12 manufactured by Matsuo Sangyo Co., Ltd. On the other hand, a conductive layer was formed by applying hot air at 80 ° C. for 60 seconds from the direction of 90 ° and drying by heating to obtain a conductive laminate. By changing the number of the bar coater and changing the coating amount of the silver nanowire / additive mixture dispersion (conductive composition), this conductive laminate decreases the average value A of the opening area and its variation deviation σ. The surface resistance value was lower than that of Example 5 before the change.

(Example 8)
A conductive layer was formed in the same manner as in Example 7 except that the substrate B was used, and this was used as a conductive laminate. In this conductive laminate, the average value A of the opening area and the variation deviation σ thereof are reduced by changing the type of the hydrophilic base material, and the surface resistance value is higher than that in Example 7 using the base material C having a different hydrophilic layer. Decreased.

Example 9
The silver nanowire / additive mixture dispersion of Example 2 was prepared.

  Next, this silver nanowire / additive mixture dispersion (conductive composition) was applied to one side of the base material B using a bar coater count 14 manufactured by Matsuo Sangyo Co., Ltd. On the other hand, a conductive layer was formed by applying hot air at 80 ° C. for 60 seconds from the direction of 90 ° and drying by heating to obtain a conductive laminate. By changing the number of the bar coater and changing the coating amount of the silver nanowire / additive mixture dispersion (conductive composition), this conductive laminate decreases the average value A of the opening area and its variation deviation σ. The surface resistance value was lower than that of Example 8 before the change.

(Example 10)
The silver nanowire / additive mixture dispersion of Example 2 was prepared.

  Next, this silver nanowire / additive mixture dispersion (conductive composition) was applied to one side of the substrate B using a bar coater count 16 manufactured by Matsuo Sangyo Co., Ltd. On the other hand, a conductive layer was formed by applying hot air at 80 ° C. for 60 seconds from the direction of 90 ° and drying by heating to obtain a conductive laminate. By changing the number of the bar coater and changing the coating amount of the silver nanowire / additive mixture dispersion (conductive composition), this conductive laminate decreases the average value A of the opening area and its variation deviation σ. The surface resistance value was lower than that of Example 9 before the change.

(Example 11)
The silver nanowire / additive mixture dispersion of Example 2 was prepared.

  Next, this silver nanowire / additive mixture dispersion (conductive composition) was applied to one side of the substrate B using a bar coater count 20 manufactured by Matsuo Sangyo Co., Ltd. On the other hand, a conductive layer was formed by applying hot air at 80 ° C. for 90 seconds from the direction of 90 ° and drying by heating to obtain a conductive laminate. In this conductive laminate, the average value A of the opening area and its variation are changed by changing the count of the bar coater and changing the coating time of the silver nanowire / additive mixture dispersion (conductive composition) and also the drying time. The deviation σ decreased, and the surface resistance value was lower than that of Example 10 before the change.

(Example 12)
The silver nanowire / additive mixture dispersion of Example 2 was prepared.

  Next, this silver nanowire / additive mixture dispersion (conductive composition) was applied to one side of the substrate B using a bar coater count 24 manufactured by Matsuo Sangyo Co., Ltd. On the other hand, a conductive layer was formed by applying hot air of 80 ° C. from a direction of 90 ° for 120 seconds and drying by heating to obtain a conductive laminate. In this conductive laminate, the average value A of the opening area and its variation are changed by changing the count of the bar coater and changing the coating time of the silver nanowire / additive mixture dispersion (conductive composition) and also the drying time. The deviation σ decreased, and the surface resistance value was lower than that of Example 11 before the change.

(Example 13)
The silver nanowire / additive mixture dispersion of Example 2 was prepared.

  Next, this silver nanowire / additive mixture dispersion (conductive composition) was applied to one side of the substrate B using a bar coater count 28 manufactured by Matsuo Sangyo Co., Ltd. On the other hand, a conductive layer was formed by applying hot air of 80 ° C. from a direction of 90 ° for 120 seconds and drying by heating to obtain a conductive laminate. By changing the number of the bar coater and changing the coating amount of the silver nanowire / additive mixture dispersion (conductive composition), this conductive laminate decreases the average value A of the opening area and its variation deviation σ. The surface resistance value was lower than that of Example 12 before the change.

(Example 14)
Using conductive material D, acrylic resin (“Follet” (registered trademark) GS-1000, solid content concentration 30 mass%, manufactured by Soken Chemical Co., Ltd.) as a binder component is 60 mass% with respect to the total solid content. (Solid content mixing ratio: binder component / conductive material = 40% by mass / 60% by mass), and then adjusting the concentration by adding ethyl acetate to this mixed solution so that the solid content of the paint is 50% by mass, An acicular silicon dioxide-based / ATO (antimony-doped tin oxide) composite compound dispersion was obtained.

  Next, this acicular silicon dioxide-based / ATO (antimony-doped tin oxide) composite compound dispersion was applied to one side of the substrate B using a slit die coat equipped with a shim made of sus (shim thickness 100 μm), A conductive layer was formed on the coated surface by applying hot air of 120 ° C. from a direction of 30 ° to the coating direction for 300 seconds and drying by heating to obtain a conductive laminate. In this conductive laminate, the surface resistance value and the optical characteristics can be adjusted by changing the conductive material from Examples 1 to 13.

(Example 15)
A conductive layer was formed in the same manner as in Example 14 except that hot air of 80 ° C. was applied for 300 seconds from a direction 90 ° to the coating direction on the coated surface, and this was used as a conductive laminate. Even when a conductive material different from those in Examples 1 to 13 is used, this conductive laminate has the effect of reducing the average value A of the opening area and its variation deviation σ by changing the conditions at the time of heating and drying to preferable conditions. As a result, the surface resistance value was lower than that of Example 14 before the change.

(Example 16)
A copper nanowire dispersion was obtained in the same manner as in Example 1 except that the conductive material B was used. Next, the same silver nanowire dispersion coating liquid as in Example 1 and the copper nanowire dispersion coating liquid were mixed so that the mass ratio was silver nanowire dispersion coating liquid: copper nanowire dispersion coating liquid = 6: 4. Then, a silver nanowire / copper nanowire mixed conductive material dispersion coating liquid was obtained.

  Next, this silver nanowire / copper nanowire mixed conductive material dispersion coating liquid (mixed conductive composition) was applied to one side of the substrate B using a bar coater count 9 manufactured by Matsuo Sangyo Co., Ltd. A conductive layer was formed on the surface by applying hot air of 120 ° C. from a direction of 30 ° to the coating direction for 60 seconds and drying by heating to obtain a conductive laminate. This conductive laminate was able to adjust the surface resistance value and optical characteristics by mixing different conductive materials with the conductive materials of Examples 1-13.

(Example 17)
The same silver nanowire / additive mixture dispersion as in Example 2 and the same copper nanowire dispersion as in Example 16 were combined into a silver nanowire / additive mixture dispersion: copper nanowire dispersion coating liquid = 6: 4 was mixed so as to have a mass ratio to obtain a silver nanowire / copper nanowire / additive mixed conductive material dispersion coating solution.

  Next, this silver nanowire / copper nanowire / additive mixed conductive material dispersion coating liquid (mixed conductive composition) was applied to one side of the substrate B using a bar coater count 9 manufactured by Matsuo Sangyo Co., Ltd. A conductive layer was formed by applying hot air at 80 ° C. for 60 seconds from the direction of 90 ° to the coated surface for 60 seconds to form a conductive laminate. This conductive laminate includes the compound having the structure of the structural formula (1) in the molecule in the conductive layer even when the same mixed conductive material as in Example 16 is used. By changing to, an effect of reducing the average value A of the opening area and its variation deviation σ was obtained, and the surface resistance value was lower than that of Example 16 before the change.

(Example 18)
Matrix material A (50.0 g) and ethyl acetate (2268 g) were mixed and stirred to prepare a matrix composition.

Next, the matrix composition was applied using a slit die coat with a shim material (shim thickness 50 μm) mounted on the conductive layer side of Example 8, dried at 120 ° C. for 2 minutes, and then irradiated with ultraviolet rays at 80 mJ / cm ^2. Irradiation and curing were performed to form a conductive layer containing a matrix having a matrix thickness of 120 nm, and this was used as a conductive laminate. By including a matrix in the conductive layer, durability was improved as compared with Example 8.

(Example 19)
A conductive layer including a matrix having a matrix thickness of 120 nm was formed on the conductive layer side of Example 13 in the same manner as in Example 18, and this was used as a conductive laminate. By including a matrix in the conductive layer, durability was improved as compared with Example 13.

(Comparative Example 1)
The base material B was not provided with a conductive layer, and only the base material was used.

(Comparative Example 2)
As an aqueous dispersion containing the conductive material A, a silver nanowire dispersion (CleraOhm Ink-A AQ manufactured by Cambrios, USA) was prepared. In this silver nanowire dispersion liquid, a silver nanowire dispersion coating liquid was prepared so that the concentration of silver nanowires was 0.0084% by mass (the amount of silver nanowires was 1/5 with respect to Example 1).

  Next, this silver nanowire-dispersed coating liquid (conductive composition) was applied to one side of the substrate B using a bar coater count 9 manufactured by Matsuo Sangyo Co., Ltd., and the applied surface was 90 ° with respect to the coating direction. The conductive layer was formed by applying hot air of 80 ° C. for 60 seconds from the direction of the above and drying by heating. In the coating layer of the conductive material obtained under these conditions, the silver nanowires did not have a network structure, and the laminate of this comparative example did not exhibit conductivity. Therefore, the average value A of the opening area and the variation deviation σ Evaluation of was not carried out.

(Comparative Example 3)
As an aqueous dispersion containing the conductive material A, a silver nanowire dispersion (CleraOhm Ink-A AQ manufactured by Cambrios, USA) was prepared. In this silver nanowire dispersion liquid, a silver nanowire dispersion coating liquid was prepared so that the concentration of silver nanowires was 0.0042% by mass (the amount of silver nanowires was 1/10 with respect to Example 1).

  Next, this silver nanowire dispersion coating liquid (conductive composition) was applied to one side of the substrate A using a bar coater count 80 manufactured by Matsuo Sangyo Co., Ltd., and the applied surface was 30 ° to the coating direction. A conductive layer was formed by applying hot air at 180 ° C. for 600 seconds from the direction of heating and drying by heating to obtain a conductive laminate.

  Silver nanowires had a network structure in the conductive material coating layer obtained under these conditions, but the conductive laminate of this comparative example had an average value A and variation deviation of the opening area in the openings of the network structure. Both σ were large values, and the surface resistance value was high and the conductivity was low compared to the conductive laminates of Examples using silver nanowires.

(Comparative Example 4)
As an aqueous dispersion containing the conductive material A, a silver nanowire dispersion (CleraOhm Ink-A AQ manufactured by Cambrios, USA) was prepared. In this silver nanowire dispersion liquid, a silver nanowire dispersion coating liquid was prepared so that the concentration of silver nanowires was 0.0084% by mass (the amount of silver nanowires was 1/5 with respect to Example 1).

  Next, this silver nanowire-dispersed coating liquid (conductive composition) was applied to one side of the base material A using a bar coater count 50 manufactured by Matsuo Sangyo Co., Ltd., and the applied surface was 90 ° to the coating direction. A conductive layer was formed by applying hot air at 180 ° C. for 600 seconds from the direction of heating and drying by heating to obtain a conductive laminate.

  In the conductive material coating layer obtained under these conditions, the silver nanowires had a network structure, but the conductive laminate of this comparative example had a large variation deviation σ of the opening area at the opening of the network structure. Thus, the conductive laminate of the example using silver nanowires had a high surface resistance and low conductivity.

(Comparative Example 5)
Using a bar coater count 40 manufactured by Matsuo Sangyo Co., Ltd., coated on one side of the base material A, and heated and dried by applying hot air of 80 ° C. from 90 ° to the coated surface for 600 seconds. Except for the above, a conductive layer was formed in the same manner as in Comparative Example 4, and this was used as a conductive laminate.

  In the conductive material coating layer obtained under these conditions, the silver nanowires had a network structure, but the conductive laminate of this comparative example had a large average value A of the opening area in the openings of the network structure. Thus, the conductive laminate of the example using silver nanowires had a high surface resistance and low conductivity.

(Comparative Example 6)
A silver nanowire-dispersed coating liquid having a concentration of silver nanowires of Comparative Example 4 of 0.0084% by mass (the amount of silver nanowires is 1/5 relative to Example 1) was prepared. In this silver nanowire dispersion coating liquid, additive A was mixed so that the component amount of additive A was 86 parts by mass with respect to 100 parts by mass of silver nanowires to obtain a silver nanowire / additive mixed dispersion. .

  Next, this silver nanowire / additive mixture dispersion (conductive composition) was applied to one side of the substrate A using a bar coater count 50 manufactured by Matsuo Sangyo Co., Ltd. On the other hand, a conductive layer was formed by applying hot air of 150 ° C. from a direction of 150 ° for 600 seconds and drying by heating to obtain a conductive laminate.

  In the conductive material coating layer obtained under these conditions, the silver nanowires had a network structure, but the conductive laminate of this comparative example had a large variation deviation σ of the opening area at the opening of the network structure. Thus, the conductive laminate of the example using silver nanowires had a high surface resistance and low conductivity.

(Comparative Example 7)
The concentration was adjusted by adding water so that the concentration of the conductive material D would be the same as in Example 14 without using the acrylic resin as the binder component in Example 14, and the acicular silicon dioxide-based ATO (antimony) A dope tin oxide) composite compound dispersion was obtained.

  Next, this acicular silicon dioxide-based / ATO (antimony-doped tin oxide) composite compound dispersion was applied to one side of the substrate A using a slit die coat equipped with a shim made of sus (sim thickness 100 μm), A conductive layer was formed by applying hot air of 150 ° C. from the direction of 0 ° to the coated surface for 300 seconds and drying by heating to obtain a conductive laminate.

  In the conductive material coating layer obtained under these conditions, the acicular silicon dioxide-based / ATO (antimony-doped tin oxide) composite compound had a network structure, but the conductive laminate of this comparative example had a network structure. Both the average value A and the variation deviation σ of the opening area in the opening are large, and the surface resistance value is higher than that of the conductive laminate of the example using the acicular silicon dioxide-based / ATO (antimony-doped tin oxide) composite compound. The conductivity was low.

  In any of the examples, a conductive laminate showing good conductivity was obtained. When the conductive layer further contains a compound having the structure of the structural formula (1) in the molecule together with the linear structure as in Example 2, or a substrate having a hydrophilic layer as in Example 3 was applied. In this case, the conductivity was further improved as compared with Example 1 when conditions where the drying process was more preferable as in Example 4 were applied. By changing the type of the hydrophilic substrate as in Examples 5 and 6 and Examples 7 and 8, or by changing the method of forming the conductive layer as in Examples 9 to 13, the surface resistance value is further reduced. In addition, the electrical conductivity can be further improved, and the optical characteristics (total light transmittance) can be adjusted.

  Examples 14 and 15 in which the components of the conductive layer are not silver nanowires, and Examples 16 and 17 using a conductive layer in which silver nanowires and linear structures other than silver nanowires are mixed, have surface resistance and optical properties. It became a result inferior compared with Examples 1-13 whose characteristic is a conductive layer of only silver nanowire.

  Further, even when formed with the same conductive material (linear structure), when the polymer layer is further included in the conductive layer as in Examples 18 and 19, it is high as in Examples 8 and 13. The durability was improved as compared with the case of the conductive layer not containing the molecular matrix.

  When the conductive layer is not provided (Comparative Example 1), or when the conductive component including the linear structure is included but does not have the network structure (Comparative Example 2), the conductivity is not exhibited. When the network structure of the conductive layer has a large opening area variation deviation σ as in Comparative Examples 4 and 6, or the average value A of the opening area in Comparative Example 5 has a large value, Even when a silver nanowire which is a conductive material (linear structure) with good conductivity was used, a conductive laminate having low conductivity was obtained. In particular, as in Comparative Example 3 and Comparative Example 7, when the average value A and the variation deviation σ of the opening area are both large, any conductive material (linear structure) has extremely low conductivity. It became.

  The conductive laminate of the present invention is suitably used for touch panel applications because of its good conductivity. Furthermore, the conductive laminate of the present invention can be suitably used for display members such as liquid crystal displays, organic electroluminescence (organic EL), and electronic paper, and electrode members used in solar cell modules and the like.

1: Base material 2: Hydrophilic base material 3: Hydrophilic layer 4: Conductive layer 5: Conductive surface observed from a direction perpendicular to the laminated surface 6: Single fibrous conductor (an example of a linear structure)
7: Aggregation of fibrous conductors (an example of a linear structure)
8: Nanowire (an example of a linear structure)
9: Needle-like conductor such as whisker (an example of a linear structure)
10: Matrix 11: Contact by overlapping fibrous conductors 12: Contact by overlapping nanowires 13: Contact by overlapping needle-like conductors such as whiskers 14: Linear structure 15 having a network structure 15: Linear structure Opening 16 formed by body network structure: conductive laminate 17 incorporated in touch panel: hydrophilic substrate 18 of conductive laminate incorporated in touch panel: conductive layer 19 of conductive laminate incorporated in touch panel: adhesive or Bonding layer 20 for laminating the conductive laminate with the adhesive: base material 21 on the screen side of the touch panel: hard coat layer 22 laminated on the base material on the screen side of the touch panel 22: conductive layer surface 23: single linear Structure 24: Single linear structure 25 existing as an aggregate 25: Aggregate 26 composed of linear structures: Diameter r of a single linear structure
27: Diameter r of a linear structure of an assembly composed of linear structures

Claims (9)

A conductive layer having a network structure composed of a linear structure on at least one surface of the substrate, and an opening satisfying the expression (1) among the opening areas of the openings formed by the network structure A conductive laminate having an average value A of 20 μm ² or less and an opening area variation deviation σ defined by the formula (2) of 26 μm ² or less.
X <Xmax × 0.9 (1)
(In the formula, X represents each opening area, and Xmax represents the maximum value of each opening area.)
σ = {(Σ (X−A) ² ) / N} ^0.5 (where Σ is i = 1 to N)
... Formula (2)
(Wherein, X is each opening area of the opening satisfying the expression (1), A is the average value of the opening area X of the opening satisfying the expression (1), and N is the total number of openings satisfying the expression (1). Show.) The conductive laminate according to claim 1, wherein the linear structure is a silver nanowire. The electrically conductive laminated body of Claim 1 or 2 which further contains the compound which has the structure of following Structural formula (1) in a molecule | numerator in the said electrically conductive layer.

(In the formula, Ra (a = 1 to 4) represents H or F. n1 and n2 each independently represents an integer of 1 to 10.) The conductive laminate according to claim 1, further comprising a polymer matrix in the conductive layer. The conductive laminate according to claim 1, wherein the substrate is a hydrophilic substrate in which a hydrophilic layer containing a compound having a hydrophilic group is laminated on at least one outermost layer. It is a manufacturing method of the electrically conductive laminated body in any one of Claims 1-5, Comprising: In the process of apply | coating the water containing dispersion liquid of a linear structure on a base material, and drying and forming a conductive layer, a drying process The manufacturing method of the electrically conductive laminated body which is the process of applying to the surface which applied the airflow whose temperature is 25-120 degreeC from the direction of 45-135 degrees with respect to an application direction. The display body containing the electrically conductive laminated body in any one of Claims 1-5. A touch panel incorporating the display body according to claim 7. An electronic paper in which the display body according to claim 7 is incorporated.

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